Schiavone, the Roland Garros winner in 2010 and runner-up to Li last year, was unlucky to run into battling American Varvara Lepchenko for the second time in a month.
Lepchenko, who beat the world number 12 on Madrid's new blue clay four weeks ago, struck again, defeating Schiavone 3-6 6-3 8-6 in the midday sun on Court One.
Seventh seed Li had to fight hard against world number 36 Christina McHale of the United States before winning 3-6 6-2 6-1 and setting up a fourth-round match against Kazakh qualifier Yaroslava Schedova.
While her rivals toiled, second seed Maria Sharapova swept past Peng Shuai of China 6-2 6-1 and has now spent eight minutes less on court in three matches than Schiavone and Lepchenko did in their single encounter.
On a hot day at Roland Garros, Russian Mikhail Youzhny melted hearts when he scrawled the word "SORRY!" in the clay with the toe of his shoe after winning only six points in the first eight games of a three-set thrashing by Spanish sixth seed David Ferrer.
"I just wanted to say sorry to the fans because they came to see a beautiful match but I simply could not give them that," Youzhny told Russian reporters after the 6-0 6-2 6-2 defeat.
MURRAY THROUGH
Fourth seed Andy Murray, who came close to withdrawing from his second-round match with a back problem on Thursday, looked a new man when he easily beat Colom bia's Santiago Giraldo 6-3 6-4 6-4 to reach the last 16.
The Briton will now play 17th seed Richard Gasquet, who beat 34-year-old German Tommy Haas - a qualifier here - 6-7 6-3 6-0 6-0.
Murray said he had felt better on Friday and had done some light practice.
"I woke up this morning again feeling better than I did, but that's because of the work my physio has done the last 48 hours and all the recovery work that we've done between the last match and now," he told a news conference.
"So obviously with the rest and doing all the right things, I felt better."
Li, who last year became the first player from an Asian nation to win a grand-slam singles title, struggled with her serve at the start and blamed herself for being too passive.
"In the first set I was always following what she did, feeling like she was the champion on the court," Li told a news conference. "She is a very dangerous player; I was happy I could win... because I had more experience."
Czech fourth seed Petra Kvitova, the Wimbledon champion, had hoped to get a swift win on the Philippe Chatrier court after taking the first set against Nina Bratchikova in 28 minutes.
The Russian upped her game however, and Kvitova needed a third set to win 6-2 4-6 6-1 and go through to a meeting with Lepchenko.
Uzbekistan-born Lepchenko was delighted to reach the fourth round of a grand-slam event for the first time. "I was fighting all the way to the end, I was trying to stay with Francesca the whole time," she told a news conference.
"She played amazing and it is her court and I knew that she was not going to give it away for free," added the left-hander, who has risen from 128 at the start of the year to 63 in the rankings. "I had to work really hard, and I did."
Italian Schiavone said she had been happy overall with the way she played but added: "I had my chances, I simply did not take them."
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